Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/48—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
  • C08K5/3435—Piperidines
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
  • Y10T428/2969—Polyamide, polyimide or polyester
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
  • Y10T442/102—Woven scrim
  • Y10T442/183—Synthetic polymeric fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/30—Woven fabric [i.e., woven strand or strip material]

Definitions

• the invention relates to improved polyamides.
• the invention inherently relates to light and heat stabilized polyamides.
• the invention relates to a process for the preparation of these polyamides and their use.
• DE-PS 39 32 912, Sandoz relates to polyamides which contain residues with sterically hindered amino groups, in particular 2,2,6,6-tetramethylpiperidyl-4 radicals in the molecule.
• the number of radicals is on average 5 to 200 per polyamide molecule.
• these polyamides u. a. for improving the dyeability of polyamides and as light stabilizers for plastics; they should be added to it in quantities of 1-10 wt .-% and in particular be mixed in the melt.
• TMP 2,2,6,6-tetramethylpiperidin-4-ol
• the triacetonediamine compound is added to the starting monomer or the polymerizing reaction mixture and is bound to the chain end of the polymer chain by reaction of its primary amino group with the starting monomers or with the carboxyl groups of the resulting polyamide.
• the secondary amino group of the triacetonediamine compound does not react because of steric hindrance.
• the triacetonediamine compound also acts as a chain regulator.
• the chemical bonding of the triacetonediamine compound to the polymer chain of the polyamide inherently stabilized polyamides are obtained.
• the process according to the invention thus offers the advantage that a separate process step otherwise required for blending in a stabilizer into the polyamide is no longer necessary. This eliminates problems or quality reductions, as in the mixing of a stabilizer after superficial application to the polyamide granules, by incompatibility, viscosity degradation, Auswandem, evaporation or washing out of the stabilizer or a double stress such. B. may arise during assembly.
• the polyamides are protected by the triacetonediamine compound against damage by heat and thermal oxidation during processing and in use.
• the polymerization or polycondensation of the starting monomers in the presence of the triacetonediamine compound is preferably carried out by the usual methods.
• the polymerization of AH salt in the presence of triacetonediamine can be carried out by the usual batch process (see: Polymerization Processes p.424-467, especially p. 444-446, Interscience, New York, 1977) or by a continuous process, e.g. B. according to EP 129 196 done.
• the triacetonediamine compound and the starting monomers can be fed separately or as a mixture to the reactor.
• the triacetonediamine compound is added according to a predetermined amount / time schedule.
• caprolactam or at least one dicarboxylic acid A selected from adipic acid, sebacic acid and terephthalic acid and at least one diamine selected from hexamethylenediamine and tetramethylenediamine, or dicarboxylic acid-diamine salts thereof are polymerized or polycondensed as starting monomers.
• Particularly preferred is caprolactam.
• Particularly preferred dicarboxylic acid A are adipic acid and terephthalic acid. With appropriate selection of the starting monomers, the polymerization or polycondensation leads to the preferred polyamides polyamide 6, polyamide 66, polyamide 46 or polyamide 610.
• the triacetonediamine compound is the starting monomers in a Amount of 0.03 to 0.8 mol%, preferably from 0.06 to 0.4 mol%, in each case based on 1 mol of acid amide groups of the polyamide added.
• This amount refers, for example, in the production of polyamide 6 to 1 mole of caprolactam or in the preparation of polyamide 66 to 0.5 mole of AH salt. It has been found that at levels less than 0.03 mole percent, adequate stabilization is not achieved, whereas at levels above 0.8 mole percent, the desired degree of polymerization is not achieved because of the control action of the triacetonediamine compound.
• the triacetonediamine compound is combined with at least one of the conventional chain regulators.
• Suitable chain regulators are z.
• monocarboxylic acids such as acetic acid, propionic acid and benzoic acid.
• the amino end group content depends on the desired dyeability of the threads or fibers.
• the melt stability depends on the practical requirements in the processing of the products, in particular in the spinning.
• the polyamide 6 (polycaprolactam) prepared by the process according to the invention contains, in addition to the triacetonediamine compound, dicarboxylic acids B as chain regulators.
• dicarboxylic acids B as chain regulators.
• the desired dyeability of the threads or fibers and good light and heat stability such products also have improved strength of the threads obtained, in particular during high-speed spinning.
• the dicarboxylic acids B used as chain regulators in combination with the triacetonediamine compound may be the same as or different from the dicarboxylic acids used as dicarboxylic acid A. They are preferably selected from: C 4 -C 10 alkanedicarboxylic acids, in particular adipic acid, azelaic acid, sebacic acid and dodecanedioic acid; C 5 -C 8 -cycloalkanedicarboxylic acids, in particular cyclohexane-1,4-dicarboxylic acid; and benzene and naphthalenedicarboxylic acids, in particular isophthalic acid, terephthalic acid and naphthalene-2,6-dicarboxylic acid.
• the dicarboxylic acids B are preferably used in an amount of 0.06 to 0.6 mol%, preferably 0.1 to 0.5 mol%, in each case based on 1 mol of acid amide groups of the polyamide.
• the polymerization or polycondensation is carried out by the process according to the invention in the presence of at least one pigment.
• Preferred pigments are titanium dioxide or coloring compounds of inorganic or organic nature.
• the pigments are preferably added in an amount of 0 to 5 parts by weight, in particular 0.02 to 2 parts by weight, in each case based on 100 parts by weight of polyamide.
• the pigments may be fed to the reactor with the starting materials or separately therefrom.
• the triacetonediamine compound also as a chain regulator component
• the light stability of the polymer is significantly improved over a polymer containing only pigment and no triacetonediamine.
• the invention also relates to the use of inventive, inherently light and heat stabilized polyamides for the production of threads, fibers or films. Furthermore, the invention relates to a process for the production of threads based on polycaprolactam by rapid spinning at take-off speeds of at least 4000 m / min and the threads produced therefrom. Moreover, the invention encompasses the use of filaments made according to the invention for the production of fibers and fabrics as well as the fibers and fabrics obtainable by this use.
• the relative viscosity of the polyamides was determined in 1% solution (1 g / 100 ml) in concentrated sulfuric acid (96% by weight) at 25 ° C.
• the determination of the end group content was carried out as an acidimetric titration.
• the amino end groups were titrated in a solution in phenol / methanol 70:30 (parts by weight) with perchloric acid.
• the carboxyl end groups were titrated in a solution in benzyl alcohol with potassium hydroxide.
• the content of the polyamides on the triacetonediamine compound and optionally on dicarboxylic acids can be determined by hydrolysis of a sample in dilute mineral acid by analysis of the hydrolyzate by customary methods, for example by gas chromatography.
• the determination of the heat resistance of the polyamide threads was carried out under conditions similar to those of heat-setting processes in subsequent treatment stages such.
• B. heat fixing (Heatsetten) of BCF (bulked continuous filament) or tenter fixation textile fabrics largely correspond. Strands of 5 g each were deducted from the drawn threads, rapidly introduced together with the comparative samples on a holding device into a convection oven preheated to 185 ° C., and left there for 120 seconds from the time the air temperature measured in the immediate vicinity of the sample was reached again. The sample is then removed immediately and cooled in air at 20 ° C room temperature. Comparative threads were treated together.
• the absolute decrease of the basic groups is then converted to a more practical assessment in a percentage decrease, based on the untreated yarn sample.
• the maximum tensile elongation at break was determined with a Uster Tensorapid I gauge, with the set length for preoriented threads (POY) 200 mm, for drawn and textured threads 500 mm.
• the test time to break the threads was in the range 20 ⁇ 2 seconds.
• the prestressing force was 0.025 cN / dtex at POY and 0.05 cN / dtex at drawn yarns.
• the polymerization reactor used was a VK tube according to EP 20946 of stainless steel, material no. 1.4541.
• the VK pipe had an operating volume of 340 l and was heated with a thermal oil.
• a mixture of 100 parts by weight of molten caprolactam, 0.5 parts by weight of water and 0.33 parts by weight of terephthalic acid was continuously fed to the VK tube at the top of the first reaction zone in an amount of 41 kg / hr with stirring.
• triacetonediamine was fed as a separate stream to the VK tube in the first reaction zone continuously in an amount of 55 ml / h.
• the concentration of triacetonediamine was thus 0.087 mol%, the concentration of terephthalic acid 0.23 mol%, each based on 1 mol of caprolactam.
• the temperature of the first reaction zone was 266 ° C; the pressure in the vapor phase over the first reaction zone was 1.5 bar absolute.
• Polycaprolactam was discharged from the bottom of the VK tube, transferred to granules, extracted with hot water and dried.
• the dried polymer had a relative viscosity of 2.70, an amino end group content of 39 meq / kg and a carboxyl end group content of 65 meq / kg.
• the product was spun at 275 ° C melt temperature on an Ems Inventa pilot spinning line at 23 g / min per nozzle from 0.2 mm hole diameter nozzles with 0.6 mm die channel length as galette POY.
• the speeds were 4520 m / min for the first duo, 4530 m / min for the second duo and 4500 m / min for the Barmag Craft winder.
• the filaments were cooled in a Barmag blower shaft with transverse blowing through a stream of air at 20 ° C / 65% relative humidity and 0.4 m / sec velocity.
• the preparation was carried out with a commercial preparation (Limanol E 100, Fa. Schill & Seilacher, 0.65% overlay on thread) via dosing pump and ceramic oiler in the blower shaft.
• the relative viscosity was 2.70, the amine end group concentration was 35, and the carboxyl end group concentration was 63 meq / kg.
• polyamide 6 of relative viscosity 2.67 without triacetonediamine was spun under identical conditions as in Example 1.
• the yarns thus obtained had a maximum tensile yield of 43%, a tenacity of 4.8 cN / dtex and a Usterreteggikeit U% (normal test) of 0.5.
• the titer was 43.8 f 12 dtex.
• the relative viscosity was 2.66, the content of amino end groups was 32 meq / kg, and at carboxyl end groups 53 meq / kg.
• the filaments were subjected to a heat treatment of 120 s in air at 185 ° C.
• Table 1 shows that the polyamides 6 according to the invention after the heat treatment show a smaller decrease in the relative viscosity and the amino group content and a smaller increase in the carboxyl group content than the polyamide of Comparative Example 1 and thus have better heat stabilization.
• Caprolactam was in the same VK tube as in Example 1 with the addition of 0.38 mol% of terephthalic acid, 0.20 mol% triacetonediamine, 0.5 wt .-% water and 0.3 wt .-% titanium dioxide (as a matting agent ) polymerized.
• the polymerization was carried out at a rate of 25 kg / h and a temperature of 255 ° C in the first reaction zone under atmospheric pressure.
• the procedure was the same as in Example 1.
• the dried product had a relative viscosity of 2.37, an amino end group content of 45 meq / kg and a carboxyl end group content of 79 meq / kg.
• the product was melted in a Barmag single-screw extruder and fed at 270 ° C melt temperature to a Barmag SP 42 spinning system. From a delivery rate of 22.6 g / min and nozzle and the use of 12-hole spinnerets with capillary holes of 0.20 mm diameter and 0.60 mm in length, a spun (POY) resulted at 4500 m / min winding speed Titer of 52f 12 dtex.
• the POY was cold stretched at 748 m / min on a Rieter J5 / 10a stretch twisting machine.
• the tension in the pre-stretch field was 0.8%, the total draw ratio was 1: 1.298.
• the drawn filaments had a maximum tensile yield of 36%, a tenacity of 5.2 cN / dtex, a titer of 44 f 12 dtex, and a U value of U% (normal test) of 0.7.
• the relative viscosity was found to be 2.41, the amino end groups 42 and the carboxyl end groups 74 meq / kg.
• polyamide 6 of relative viscosity 2.39 containing no triacetonediamine was extruded in the manner described in Example 2. Cooling and preparation of the threads were carried out as previously described. Galettenlos was wound at 4500 m / min. The POY had a maximum tensile yield of 62%, a tenacity of 4.2 cN / dtex and a boiling shrinkage of 9%.
• the POY was cold post-stretched as in Example 2, the total draw ratio in this case was 1: 1.279.
• the drawn filaments had a maximum tensile yield of 34%, a tenacity of 4.6 cN / dtex, a titer of 43.6 f 12 dtex, and a Uster U% (normal test) of 0.9.
• the relative viscosity of the filaments was 2.41, the amino end groups were determined to be 25, and the carboxyl end groups were determined to be 65 meq / kg.
• the filaments were subjected to the conditions corresponding to a textile tenter fixation (185 ° C hot air, 120 sec) and the following key figures were measured: Table 2 Example 2 Comparative Example 2 relative viscosity untreated 2.41 2.41 treated 2.28 1.84 decrease - 0.13 - 0.57 Amino groups untreated 42 25 (Meq / kg) treated 34 13 decrease - 8th - 12 Decrease (%) - 19% - 48% Carboxyl groups untreated 74 65 (Meq / kg) treated 75 93 increase +1 + 28
• the POY had a maximum tensile yield of 64%, a tenacity of 4.7 cN / dtex and a boiling shrinkage of 10%.
• the stretching was carried out under the conditions given in Example 2.
• the drawn yarns then had a maximum tensile yield of 37%, a tenacity of 5.4 cN / dtex, a boiling shrinkage of 14%, a Usterrete spakeit U% (normal test) of 0.8 and a titer of 44 f 12 dtex.
• the relative viscosity was 2.40, the amino end groups were 42 and the carboxyl end groups 74 meq / kg.
• Example 3A Example 3B Maximum tensile strength extension 64% 68% ultimate tensile strength 4.4 cN / dtex 4.2 cN / dtex boiling shrinkage 8th% 8th% Uster (normal test) U% 0.6% 0.5% titres 51 f 12 dtex 52 f 12 dtex
• the POY was then cold stretched on draw twist machines with the draw ratios: 1: 1,257 1: 1,313 and had the data: Maximum tensile strength extension 44% 38% ultimate tensile strength 5.0 cN / dtex 4.8 cN / dtex boiling shrinkage 11% 12% Uster (normal test) U% 0.6% 0.8% titres 45 f 12 dtex 43 f 12
• the polyamide 6 according to the invention shows better heat stabilization than the polyamides 6 of the comparative examples.
• Caprolactam was in the same VK tube as in Example 1 with the addition of 0.55 wt .-% (0.375 mol%) of terephthalic acid, 0.33 wt .-%. (0.239 mol%) of triacetonediamine, 0.5 wt. -% water and 0.3 wt .-% titanium dioxide polymerized.
• the polymerization was carried out at a rate of 25 kg / h and a temperature of 255 ° C in the first reaction zone under atmospheric pressure.
• the procedure was the same as in Example 1.
• the dried product had a relative viscosity of 2.42, an amino end group content of 46 meq / kg and a carboxyl end group content of 70 meq / kg.
• the content of extractables was 0.38%.
• the POY had a fineness of 52 f 12 dtex, 59% maximum tensile yield strength and a tenacity of 4.1 cN / dtex.
• the electromotive test (gap width 45 ⁇ m) measured an average of 0.5 errors / 100 km.
• Caprolactam was polymerized in the same CV tube as in Example 4 with the addition of 0.53 wt% (0.361 mol%) terephthalic acid, 0.5 wt% water and 0.3 wt% titanium dioxide. The polymerization was carried out at a temperature of 252 ° C in the first reaction zone. The procedure was the same as in Example 4. The dried product had a relative viscosity of 2.39, an amino end group content of 27 meq / kg and a carboxyl end group content of 92 meq / kg. The content of extractables was 0.32%.
• TAD triacetonediamine
• the chips thus contained the same amount of TAD in substance and practically the same terephthalic acid content (copolymerized) as described above product 4; except for the type of TAD addition, the two products agreed.
• TAD drummed TAD does not feed (completely) into the chips. They remain TAD-moist and of intense Amigeruch. This property is extremely disadvantageous in handling, and extensive safety precautions are required because TAD has a corrosive effect.
• Example 4 During the residence time in the spinning system, the viscosity builds up in Example 4, while it degrades drastically in Comparative Example 4. Also advantageous are the comparatively small change of amino groups in Example 4 and extractables (determination: 16 hours extraction with methanol at reflux) and the fact that significantly less spider smoke is produced in the nozzle area during spinning.
• Example 4 The spinning and further processing took place under the conditions listed in Example 4.
• the POY had a fineness of 52 f 12 dtex, 54% maximum tensile yield strength and a tenacity of 3.8 cN / dtex.
• Example 4 Comparative Example 4 Spider fractures / 100 kg 1.2 4.0 Elekometertest error / 100 km 0.5 7.5 Draft error / 100 kg 1.8 14.5 Warping error / 100 km 0.037 > 0.65
• the polyamide 6 of Example 4 according to the invention has lower error rates in all processing stages than the polyamide 6 of Comparative Example 4, in which TAD was blended into the polyamide in substance.
• Example 4 TAD is more fully anchored in the polyamide than in Comparative Example 4. Thus, in extraction processes (such as in dyeings), less amine is converted to the aqueous phase.
• polyamide 6 of relative viscosity 2.39 which had no triacetonediamine and was matted with 0.3% of titanium dioxide, was spun in the manner described in Comparative Example 2.
• the POY had a fineness of 51 f 12 dtex, a maximum elongation at break of 57% and a fineness-related Maximum tensile force of 3.8 cN / dtex. After cold drawing with a draw ratio of 1: 1.244, the values listed in Table 7 below were determined for the untreated sample.
• Example 7 The exposure and the measurement of the maximum tensile elongation at break and maximum tensile force were performed together with Example 5. The results are shown in Table 7.
• Caprolactam was polymerized under the conditions given in Example 4 (with the same starting materials and amounts) using the same type of titanium dioxide as in Comparative Example 5.
• the dried polyamide had a relative viscosity of 2.43, an amino end group content of 44 meq / kg and a carboxyl end group content of 71 meq / kg.
• the content of extractables was 0.36%.
• the spinning was carried out as described in Comparative Example 2 galettenlos at 4500 m / min.
• the POY had a fineness of 51 f 12 dtex, a maximum tensile strength of 61% and a tenacity of 4.3 cN / dtex.
• Table 7 clearly shows that the polyamide prepared in the presence of triacetonediamine and TiO 2 (Example 5) has a significantly improved light stability compared with a comparison polymer (Comparative Example 5) which contains only TiO 2 and no triacetonediamine.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Polyamides (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Artificial Filaments (AREA)
• Materials For Medical Uses (AREA)
• Multicomponent Fibers (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
• Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Applications Claiming Priority (5)

Publications (3)

Family

ID=25935672

Family Applications (1)

Country Status (19)

Families Citing this family (38)

Citations (2)

Family Cites Families (13)

• 1995
  • 1995-04-12 CZ CZ19963014A patent/CZ290740B6/cs not_active IP Right Cessation
  • 1995-04-12 KR KR1019960705788A patent/KR100232977B1/ko not_active Expired - Lifetime
  • 1995-04-12 RU RU96122170A patent/RU2167893C2/ru not_active IP Right Cessation
  • 1995-04-12 UA UA96114353A patent/UA41404C2/uk unknown
  • 1995-04-12 ES ES95917313T patent/ES2118594T5/es not_active Expired - Lifetime
  • 1995-04-12 CN CN95193079A patent/CN1066755C/zh not_active Expired - Lifetime
  • 1995-04-12 HU HU9602845A patent/HU214924B/hu not_active IP Right Cessation
  • 1995-04-12 AT AT95917313T patent/ATE168711T1/de not_active IP Right Cessation
  • 1995-04-12 PL PL95316758A patent/PL181986B1/pl not_active IP Right Cessation
  • 1995-04-12 AU AU23442/95A patent/AU685271B2/en not_active Ceased
  • 1995-04-12 CA CA 2187821 patent/CA2187821C/en not_active Expired - Fee Related
  • 1995-04-12 US US08/722,048 patent/US6423817B1/en not_active Expired - Lifetime
  • 1995-04-12 JP JP52669995A patent/JP2911607B2/ja not_active Expired - Lifetime
  • 1995-04-12 DE DE59502905T patent/DE59502905D1/de not_active Expired - Lifetime
  • 1995-04-12 NZ NZ284802A patent/NZ284802A/en unknown
  • 1995-04-12 WO PCT/EP1995/001349 patent/WO1995028443A1/de not_active Ceased
  • 1995-04-12 EP EP95917313A patent/EP0759953B2/de not_active Expired - Lifetime
  • 1995-04-12 BR BR9507392A patent/BR9507392A/pt not_active IP Right Cessation
• 1998
  • 1998-08-07 GR GR980401782T patent/GR3027604T3/el unknown

Patent Citations (2)

Also Published As

Similar Documents

Legal Events